US4546070A - Method for processing color photographic light-sensitive material - Google Patents

Method for processing color photographic light-sensitive material Download PDF

Info

Publication number
US4546070A
US4546070A US06/680,115 US68011584A US4546070A US 4546070 A US4546070 A US 4546070A US 68011584 A US68011584 A US 68011584A US 4546070 A US4546070 A US 4546070A
Authority
US
United States
Prior art keywords
processing
sensitive material
photographic light
color photographic
group
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
US06/680,115
Other languages
English (en)
Inventor
Shinzo Kishimoto
Shigeru Ohno
Akira Abe
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Fujifilm Holdings Corp
Original Assignee
Fuji Photo Film Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Fuji Photo Film Co Ltd filed Critical Fuji Photo Film Co Ltd
Assigned to FUJI PHOTO FILM CO., LTD. reassignment FUJI PHOTO FILM CO., LTD. ASSIGNMENT OF ASSIGNORS INTEREST. Assignors: ABE, AKIRA, KISHIMOTO, SHINZO, OHNO, SHIGERU
Application granted granted Critical
Publication of US4546070A publication Critical patent/US4546070A/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C7/00—Multicolour photographic processes or agents therefor; Regeneration of such processing agents; Photosensitive materials for multicolour processes
    • G03C7/30—Colour processes using colour-coupling substances; Materials therefor; Preparing or processing such materials
    • G03C7/42—Bleach-fixing or agents therefor ; Desilvering processes
    • G03C7/421—Additives other than bleaching or fixing agents

Definitions

  • the present invention relates to a method for processing of a silver halide color photographic light-sensitive material (hereinafter referred to as a color light-sensitive material) which comprises developing, bleaching, and fixing an exposed color light-sensitive material (hereinafter referred to as a color photographic processing method), and, more particularly, to an improved bleaching process which accelerates the bleaching function thus shortening the processing time without the occurence of precipitate formed in a bleaching bath containing a bleach accelerating agent when color light-sensitive materials are continuously processed, thus providing color photographic images having good image quality.
  • a color light-sensitive material which comprises developing, bleaching, and fixing an exposed color light-sensitive material (hereinafter referred to as a color photographic processing method)
  • an improved bleaching process which accelerates the bleaching function thus shortening the processing time without the occurence of precipitate formed in a bleaching bath containing a bleach accelerating agent when color light-sensitive materials are continuously processed, thus providing color photographic images having good image quality.
  • the fundamental steps of processing color light-sensitive materials generally include a color-developing step and a silver-removing step. That is, an exposed silver halide color photographic light-sensitive material is introduced into a color-developing step, wherein silver halide is reduced with a color-developing agent to produce silver and the oxidized color developing agent in turn reacts with a color former to give a dye image. Subsequently, the color photographic material is introduced into a silver-removing step, wherein silver having been produced in the preceding step is oxidized with an oxidizing agent (usually called a bleaching agent), and dissolved away with a silver ion-complexing agent usually called a fixing agent. Therefore, only a dye image is formed in the thus processed photographic material.
  • an oxidizing agent usually called a bleaching agent
  • actual development processing involves auxiliary steps for maintaining the photographic and physical quality of the resulting image or for improving the preservability of the image.
  • auxiliary steps for maintaining the photographic and physical quality of the resulting image or for improving the preservability of the image.
  • a hardening bath for preventing the light-sensitive layer from being excessively softened during photographic processing
  • a stopping bath for effectively stopping the developing reaction
  • an image-stabilizing bath for stabilizing the image
  • a layer removing bath for removing the backing layer on the support.
  • ferricyanides, dichromates, ferric chloride, ferric ion complex salts, persulfates, etc. are known as bleaching agents.
  • ferricyanides, dichromates and ferric chloride are good bleaching agents due to their strong oxidizing ability.
  • a bleaching solution containing ferricyanides can release poisonous cyanide by photolysis and dichromates including hexa-valent chromium compounds, both causing environmental pollution. Accordingly, the waste processing solution thereof must be made completely harmless by means of special treatment in view of environmental pollution.
  • a bleaching solution containing ferric chloride as a bleaching agent is not desirable because materials constituting vessels in which the solution is retained are liable to be corroded due to the extremely low pH and large oxidizing power of the solution.
  • iron hydroxide is precipitated in an emulsion layer during the water-washing step provided after the bleaching step, resulting in stain formation.
  • ferric ion complex salts e.g., aminopolycarboxylic acid-ferric ion complex salts, particularly iron (III) ethylene-diaminetetraacetate complex salts
  • halides e.g., bromides
  • ferric ion complex salts have a comparatively small oxidizing ability and, therefore, have insufficient bleaching power.
  • a bleaching solution containing the complex salt as a bleaching agent can attain some desirable objects when bleaching a low-speed silver halide color photographic light-sensitive material containing, for example, a silver chlorobromide emulsion as a major component.
  • bleaching agents include persulfates.
  • Persulfates are usually used in a bleaching solution together with a chloride.
  • this persulfate-containing bleaching solution has less bleaching ability than ferric ion complex salts, thus requiring a substantially long period of time for bleaching.
  • bleaching agents which do not cause environmental pollution or corrode vessels and apparatuses have only a weak bleaching ability.
  • a bleaching solution containing a bleaching agent with a weak bleaching ability particularly a ferric ion complex salt.
  • bleach accelerating agents for bleaching solutions containing a ferric ion complex salt include various mercapto compounds as described in U.S. Pat. No. 3,893,858, Japanese Patent Application (OPI) Nos. 32736/78, 57831/78, 104232/78, 124424/78, 141623/78 and 52534/79, etc.; compounds having a disulfide bond as described in British Patent No. 1,337,346, Japanese Patent Application (OPI) Nos. 95630/78 and 95631/78, etc.; thiazolidine derivatives as described in Japanese Patent Publication No. 9854/78, Japanese Patent Application No. 88938/83 (corresponding to U.S. Ser. No.
  • the above-described precipitate is likely to occur when color light-sensitive materials for photographing comprising an emulsion containing silver iodobromide as a major component and large amount of silver are continuously processed with a low level replenishment or when a reproduced bleaching solution is used.
  • An object of the present invention is to provide a method for processing a color light-sensitive material which has excellent bleaching speed and which can provide color photographic images having good quality without the formation of precipitate in a bleaching solution containing a bleach accelerating agent when color light-sensitive materials are continuously processed.
  • Another object of the present invention is to provide a color photographic processing method which uses a compound having a low toxic character and which meets the requirement of preventing environmental pollution.
  • a further object of the present invention is to provide a color photographic processing method involving a bleaching step in which an enhanced bleaching ability is attained without deteriorating other photographic properties and a bleaching solution having good stability is used using a bleaching agent having a weak bleaching ability, in particular a ferric ion complex salt.
  • a bath of the bleach processing contains (a) at least one bleach accelerating agent selected from a compound having a mercapto group or a disulfide bond, a thiazolidine derivative and an isothiourea derivative and (b) at least one compound represented by the following general formula (I-a) or (I-b): ##STR2## wherein M represents a hydrogen atom, an alkali metal atom or an ammonium ion; R represents a hydrogen atom, a substituted or unsubstituted alkyl group, --SO 3 M 1 or --COOM 1 ; R 1 represents --SO 3 M 1 or --COOM 1 ; M 1 represents a hydrogen atom, an alkali metal atom or an ammonium ion; and n represents an integer
  • the substituted or unsubstituted alkyl group represented by R is preferably a substituted or unsubstituted alkyl group having from 1 to 6 carbon atoms including, for example, a methyl group, an ethyl group, a propyl group, a carboxymethyl group, etc.
  • Examples of the alkali metal atom represented by M or M 1 include a lithium atom, a sodium atom, a potassium atom, etc.
  • Examples of the substituent for the alkyl group represented by R include a sulfonic acid group, a carboxylic acid group, a hydroxy group, etc.
  • the compounds represented by the general formula (I-a) or (I-b) used in the present invention are known as examples of bleach accelerating agents as described in Japanese Patent Application (OPI) No. 28426/78. However, these compounds only have insufficient bleach accelerating effects and thus can not achieve the purpose of accelerating the bleaching step. On the other hand, the compounds represented by the general formula (I-a) or (I-b) surprisingly function to prevent the occurrence of precipitation which is formed by continuous processing of color light-sensitive materials in a bleaching solution containing the bleach accelerating agents used in the present invention, when they are used together with the bleach accelerating agents which have sufficient bleach accelerating effects.
  • the amount of the compound represented by the general formula (I-a) or (I-b) according to the present invention to be added to the bleaching solution varies depending upon the kind of processing solution, kind of photographic material to be processed, processing temperature, etc. However, an amount of about 1 ⁇ 10 -5 to about 1 ⁇ 10 -1 mol per liter of a processing solution is suitable, with 1 ⁇ 10 -4 to 5 ⁇ 10 -2 mol being preferable, and 2 ⁇ 10 -4 to 1 ⁇ 10 -2 mol being more preferable.
  • the compounds having a mercapto group or a disulfide bond, the thiazolidine derivatives and the isothiourea derivatives which are used as bleach accelerating agents in the present invention can be those having sufficient bleach accelerating effects.
  • Preferred examples of these compounds include those represented by the general formula (II) to (VIII) described below and thioglycerol and cysteine.
  • R 2 and R 3 which may be the same or different, each represents a hydrogen atom, a substituted or unsubstituted lower alkyl group or an acyl group (preferably having from 1 to 3 carbon atoms, for example, an acetyl group, a propionyl group, etc.) or R 2 and R 3 may bond to each other to form a ring; and n represents an integer of 1 to 3. It is particularly preferred that R 2 and R 3 each represents a substituted or unsubstituted lower alkyl group.
  • R 4 and R 5 each has the same meaning for R 2 and R 3 as defined in the general formula (II) or R 4 and R 5 may bond to each other to form a ring; and n represents an integer of 1 to 3. It is particularly preferred that R 4 and R 5 each represents a substituted or unsubstituted lower alkyl group.
  • R 6 represents a hydrogen atom, a halogen atom (for example, a chlorine atom, a bromine atom, etc.), an amino group, a substituted or unsubstituted lower alkyl group (preferably having from 1 to 5 carbon atoms and particularly preferred examples being a methyl group, an ethyl group and a propyl group) or alkyl-substituted amino group (for example, a methylamino group, an ethylamino group, a dimethylamino group, a diethylamino group, etc.).
  • a halogen atom for example, a chlorine atom, a bromine atom, etc.
  • an amino group preferably having from 1 to 5 carbon atoms and particularly preferred examples being a methyl group, an ethyl group and a propyl group
  • alkyl-substituted amino group for example, a methylamino group, an ethylamino group,
  • R 7 and R 8 which may be the same or different, each represents a hydrogen atom, an alkyl group which may be substituted (preferably a lower alkyl group, for example, a methyl group, an ethyl group, a propyl group, etc.), a phenyl group which may be substituted or a heterocyclic group which may be substituted (more specifically a group derived from a heterocyclic ring containing at least one hetero atom such as a nitrogen atom, an oxygen atom, a sulfur atom, etc., for example, a pyridine ring, a thiophene ring, a thiazolidine ring, a benzoxazole ring, a benzotriazole ring, a thiazole ring, an imidazole ring, etc.); R 9 represents a hydrogen atom or a lower alkyl group which may be substituted (preferably having from 1 to 3 carbon atoms, for example,
  • R 7 to R 9 examples of the substituents included in R 7 to R 9 are a hydroxy group, a carboxy group, a sulfo group, an amino group, a lower alkyl group, etc.
  • R 11 , R 12 and R 13 which may be the same or different, each represents a hydrogen atom or a lower alkyl group (preferably having from 1 to 3 carbon atoms, for example, a methyl group, an ethyl group, etc.) or R 11 and R 12 or R 11 and R 13 may bond to each other to form a ring
  • X represents an amino group which may be substituted (examples of the substituents include a lower alkyl group such as a methyl group, etc., an alkoxyalkyl group such as an acetoxymethyl group, etc.), a sulfonic acid group or a carboxy group
  • n represents an integer of 1 to 3. It is particularly preferred that R 11 to R 13 each represents a hydrogen atom, a methyl
  • the bleach accelerating agents represented by the general formula (II) or (III) are particularly preferred since the bleach accelerating effects are further improved when the agents are used in combination with the compound represented by the general formula (I-a) or (I-b) in comparison with the case wherein the bleach accelerating agents are used alone.
  • the above-described compounds can be synthesized by known methods. More specifically, the compounds represented by the general formula (II) can be synthesized with reference to the methods as described in U.S. Pat. No. 4,285,984, G. Schwarzenbach et al., Helv. Chim. Acta., Vol. 38, page 1147 (1955), and R. O. Clinton et al., J. Am. Chem. Soc., Vol. 70, page 950 (1948); the compounds represented by the general formula (III) can be synthesized with reference to the methods as described in Japanese Patent Application (OPI) No.
  • the compounds represented by the general formulae (IV) and (V) can be synthesized with reference to the method as described in Japanese Patent Application (OPI) No. 52534/79; the compounds represented by the general formula (VI) can be synthesized with reference to the methods as described in Japanese Patent Application (OPI) Nos. 68568/76, 70763/76 and 50169/78; the compounds represented by the general formula (VII) can be synthesized with reference to the methods as described in Japanese Patent Publication No. 9854/78 and Japanese Patent Application No. 88938/83 (corresponding to U.S. Ser. No. 612,173 filed on May 21, 1984); and the compounds represented by the general formula (VIII) can be synthesized with reference to the methods as described in Japanaese Patent Application (OPI) No. 94927/78.
  • the amount of the compounds having a mercapto group or a disulfide bond in their molecules, thiazolidine derivatives or isothiourea derivatives according to the present invention to be added to the bleaching solution varies depending upon the kind of processing solution, kind of photographic material to be processed, processing temperature, time necessary for conducting intended processing, etc. However, an amount of about 1 ⁇ 10 -5 to about 10 -1 mol per liter of a processing solution is suitable, with 1 ⁇ 10 -4 to 5 ⁇ 10 -2 mol being preferable.
  • the compounds (I-a), (I-b) and bleach accelerating agents according to the present invention are generally added to a processing solution by previously dissolving them in water, an alkali, an organic acid, an organic solvent, or the like. If necessary, the compounds (I-a) and (I-b) and bleach accelerating agents may be directly added to the bleaching solution in the form of powder without adversely affecting their bleach accelerating effects and their effects for preventing the formation of insoluble precipitate.
  • a bleaching agent with weak bleaching power is used.
  • a ferric ion complex one of the bleaching agents, is a complex of ferric ion and a chelating agent such as an aminopolycarboxylic acid, an aminopolyphosphonic acid or the salt thereof.
  • Aminopolycarboxylic acid salts or aminopolyphosphonic acid salts are alkali metal salts, ammonium salts or water-soluble amine salts of aminopolycarboxylic acids or aminopolyphosphonic acids.
  • the alkali metals include sodium, potassium, lithium, etc.
  • water-soluble amines include alkylamines (e.g., methylamine, diethylamine, triethylamine, butylamine, etc.).
  • alkylamines e.g., methylamine, diethylamine, triethylamine, butylamine, etc.
  • alicyclic amines e.g., cyclohexylamine
  • arylamines e.g., aniline, m-toluidine, etc.
  • heterocyclic amines e.g., pyridine, morpholine, piperidine, etc.
  • Typical examples of the chelating agents of these aminopolycarboxylic acids, aminopolyphosphonic acids, and the salts thereof are:
  • Trisodium ethylenediamine-N-( ⁇ -oxyethyl)-N,N',N'-triacetate Trisodium ethylenediamine-N-( ⁇ -oxyethyl)-N,N',N'-triacetate
  • Triammonium ethylenediamine-N-( ⁇ -oxyethyl)-N,N',N'-triacetate Triammonium ethylenediamine-N-( ⁇ -oxyethyl)-N,N',N'-triacetate
  • the present invention is not limited to the above-illustrated chelating agents.
  • the ferric ion complex salts may be used in the form of the complex salt or may be formed in situ in a solution by using a ferric salt (e.g., ferric sulfate, ferric chloride, ferric nitrate, ferric ammonium sulfate or ferric phosphate, etc.) and a chelating agent (e.g., aminopolycarboxylic acid, aminopolyphosphonic acid or phosphonocarboxylic acid, etc.). When they are used in the form of a complex salt, they may be used alone or in combination of two or more.
  • a ferric salt e.g., ferric sulfate, ferric chloride, ferric nitrate, ferric ammonium sulfate or ferric phosphate, etc.
  • a chelating agent e.g., aminopolycarboxylic acid, aminopolyphosphonic acid or phosphonocarboxylic acid, etc.
  • ferric salts may be used.
  • one, two or more chelating agents may also be used.
  • a chelating agent may be used in an amount more than is necessary for forming a ferric ion complex salt.
  • a bleaching solution containing the above-described ferric ion complex may further contain complexes of other metals than iron such as cobalt or copper or hydrogen peroxide.
  • the bleaching solution according to the present invention can contain re-halogenating agents such as bromides (e.g., potassium bromide, sodium bromide, ammonium bromide, etc.), chlorides (e.g., potassium chloride, sodium chloride, ammonium chloride, etc.), and the like in addition to the bleaching agents such as ferric ion complex salts, etc. and the above-described compounds.
  • re-halogenating agents such as bromides (e.g., potassium bromide, sodium bromide, ammonium bromide, etc.), chlorides (e.g., potassium chloride, sodium chloride, ammonium chloride, etc.), and the like in addition to the bleaching agents such as ferric ion complex salts, etc. and the above-described compounds.
  • additives which have a pH-buffering ability such as inorganic acids, organic acids, or the salts thereof which are known to be used in ordinary bleaching solutions (e.g., boric acid, borax, sodium metaborate, acetic acid, sodium acetate, sodium carbonate, potassium carbonate, phosphorous acid, phosphoric acid, sodium phosphate, citric acid, sodium citrate, tartaric acid, etc.) may be added.
  • inorganic acids, organic acids, or the salts thereof which are known to be used in ordinary bleaching solutions e.g., boric acid, borax, sodium metaborate, acetic acid, sodium acetate, sodium carbonate, potassium carbonate, phosphorous acid, phosphoric acid, sodium phosphate, citric acid, sodium citrate, tartaric acid, etc.
  • the amount of bleaching agent is from about 0.1 to about 2 mols per liter of the bleaching solution, and the pH of the bleaching solution is desirably from about 3.0 to about 8.0, particularly from 4.0 to 7.0, when a ferric ion complex salt is used.
  • Primary aromatic amine color developing agents to be used in the present invention in a color developing solution include a wide range of known ones for use in various color photographic processes.
  • the developing agents include aminophenol derivativess and p-phenylenediamine derivatives. These compounds are generally used in the form of salts such as hydrochlorides or sulfates rather than in free form in view of stability. They are generally used in an amount of from about 0.1 g to about 30 g, more preferably from about 1 g to about 15 g, per liter of color developing solution.
  • the aminophenol type developing agents include, for example, o-aminophenol, p-aminophenol, 5-amino-2-hydroxytoluene, 2-amino-3-hydroxytoluene, 2-hydroxy-3-amino-1,4-dimethylbenzene, etc.
  • Particularly useful primary aromatic amine type color developing agents are N,N-dialkyl-p-phenylenediamine compounds wherein the alkyl group and the phenyl group may or may not be substituted.
  • particularly useful compounds are N,N-diethyl-p-phenylenediamine hydrochloride, N-methyl-p-phenylenediamine hydrochloride, N,N-dimethyl-p-phenylenediamine hydrochloride, 2-amino-5-(N-ethyl-N-dodecylamino)toluene, N-ethyl-N- ⁇ -methanesulfonamidoethyl-3-methyl-4-aminoaniline sulfate, N-ethyl-N- ⁇ -hydroxyethylaminoaniline, 4-amino-3-methyl-N,N-diethylaniline, 4-amino-N-(2-methoxyethyl)-N-ethyl-3
  • the alkaline color developing solution to be used in the present invention can optionally contain, in addition to the above-described primary aromatic amine color developing agent, various ingredients usually added to a color developing solution, such as alkali agents (e.g., sodium hydroxide, sodium carbonate, potassium carbonate, etc.), alkali metal sulfites, alkali metal bisulfites, alkali metal thiocyanates, alkali metal halides, benzyl alcohol, water-softening agents, thickening agents, etc.
  • alkali agents e.g., sodium hydroxide, sodium carbonate, potassium carbonate, etc.
  • alkali metal sulfites e.g., sodium hydroxide, sodium carbonate, potassium carbonate, etc.
  • alkali metal sulfites e.g., sodium hydroxide, sodium carbonate, potassium carbonate, etc.
  • alkali metal sulfites e.g., sodium hydroxide, sodium carbonate, potassium carbonate, etc.
  • the process of the present invention is applicable to color reversal processing.
  • a black-and-white developing solution to be used in this processing a black-and-white first developing solution used for reversal processing of color photographic light-sensitive materials or that to be used for processing black-and-white photographic light-sensitive materials can be used.
  • various well known additives generally added to a black-and-white developing solution can be incorporated in the solution.
  • Typical additives include developing agents such as 1-phenyl-3-pyrazolidone, metol, and hydroquinone; preservatives such as sulfites; accelerating agents comprising an alkali such as sodium hydroxide, sodium carbonate, or potassium carbonate; inorganic or organic inhibitors such as potassium bromide, 2-methylbenzimidazole, methylbenzothiazole, etc.; water-softening agents such as polyphosphoric acid salts; and slight amounts of development restrainers comprising an iodide or a mercapto compound.
  • developing agents such as 1-phenyl-3-pyrazolidone, metol, and hydroquinone
  • preservatives such as sulfites
  • accelerating agents comprising an alkali such as sodium hydroxide, sodium carbonate, or potassium carbonate
  • inorganic or organic inhibitors such as potassium bromide, 2-methylbenzimidazole, methylbenzothiazole, etc.
  • water-softening agents such as polyphosphoric acid salt
  • Silver halide color photographic light-sensitive materials to be processed according to the present invention in the presence of the compound according to the present invention are known color photographic light-sensitive materials.
  • the present invention is particularly advantageous for processing coupler-containing multilayer negative color photographic light-sensitive materials or color print photographic light-sensitive materials or for processing color photographic light-sensitive materials designed to be subjected to reversal color processing.
  • color X-ray photographic light-sensitive materials, monolayer special color photographic light-sensitive materials, and color photographic light-sensitive materials containing a black-and-white developing agents such as a 3-pyrazolidone as described in U.S. Pat. Nos. 2,751,297 and 3,902,905, Japanese Patent Application (OPI) Nos.
  • any of silver bromide, silver iodobromide, silver iodochlorobromide, silver chlorobromide, and silver chloride may be used as a silver halide.
  • the photographic emulsion to be used in the present invention can be prepared by the processes as described in P. Glafkides, Chimie et Physique Photographique (Paul Montel, 1967), G. F. Duffin, Photographic Emulsion Chemistry (The Focal Press, 1966), V. L. Zelikman et al., Making and Coating Photographic Emulsion (The Focal Press, 1964), etc.
  • cadmium salts zinc salts, lead salts, thallium salts, iridium salts or the complex salts thereof, rhodium salts or the complex salts thereof, iron salts or the complex salts thereof, etc., may be allowed to coexist.
  • both negative emulsions forming surface latent images and direct reversal emulsions can be used.
  • examples of the latter emulsions include emulsions forming internal latent images and previously fogged direct reversal emulsions.
  • Silver halide emulsions may be used as so-called primitive emulsions without conducting chemical sensitization, but are usually chemically sensitized. Chemical sensitization can be conducted according to the processes described in the above-described books by Glafkides or Zelikman et al. or in H. Fireser, Die Unen der Photographischen Too mit Silberhalogeniden (Akademische Verlagsgesellschaft, 1968).
  • sulfur sensitization using sulfur-containing compounds capable of reacting with silver ion or active gelatin, reduction sensitization using a reductive substance, and noble metal sensitization using compounds of noble metals such as gold or etc. can be employed alone or in combination.
  • useful sulfur sensitizers include thiosulfates, thioureas, thiazoles, rhodanines, and other compounds.
  • useful reduction sensitizers include stannous salts, amines, hydrazine derivatives, formamidinesulfinic acids and silane compounds.
  • complexes of the group VIII metals in the Periodic Table such as platinum, iridium, palladium, etc., can be used as well as gold complexes.
  • Photographic emulsions may be spectrally sensitized with methine dyes or the like.
  • Dyes to be used include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes, and hemioxonol dyes.
  • Particularly useful dyes are those belonging to cyanine dyes, merocyanine dyes, and complex merocyanine dyes.
  • a substantially light-insensitive, fine grain silver halide emulsion layer for the purpose of improving graininess or sharpness or for other purposes can be included.
  • Such substantially light-insensitive, fine grain emulsion layer can be provided on the light-sensitive silver halide emulsion layer or between the light-sensitive silver halide emulsion layer and a colloidal silver layer (yellow filter layer or antihalation layer).
  • the light-sensitive material according to the present invention may contain a polyalkylene oxide or its ether, ester or amine derivatives, a thioether compound, a thiomorpholine, a quaternary ammonium salt compound, a urethane derivative, a urea derivative, an imidazole derivative, a 3-pyrazolidone, etc., for the purpose of increasing sensitivity or contrast or for accelerating development.
  • gelatin As binders for photographic emulsion layers or other constituent layers gelatin is advantageously employed, but other hydrophilic colloids may also be used.
  • antifoggants or stabilizers Various compounds may be incorporated in the light-sensitive material according to the present invention as antifoggants or stabilizers. That is, many compounds known as antifoggants or stabilizers such as azoles (e.g., benzothiazolium salts, nitroindazoles, triazoles, benzotriazoles, benzimidazoles (particularly, nitro- or halogen-substituted derivatives), etc.); heterocyclic mercapto compounds (e.g., mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, mercaptotetrazoles (e.g., 1-phenyl-5-mercaptotetrazole), and mercaptopyrimidines); heterocyclic mercapto compounds having a water-soluble group such as a carboxy group or a sulfo group; thioketo compounds (e.g
  • the photographic light-sensitive material according to the present invention may contain an organic or inorganic hardener in its photographic emulsion layers or other constituent layers.
  • an organic or inorganic hardener for example, chromium slats (e.g., chromium alum, chromium acetate, etc.), aldehydes (e.g., formaldehyde, glyoxal, glutaraldehyde, etc.), N-methylol compounds (e.g., dimethylolurea, methyloldimethylhydantoin, etc.), dioxane derivatives (e.g., 2,3-dihydroxydioxane, etc.), active vinyl compounds (e.g., 1,3,5-triacryloylhexahydro-s-triazine, 1,3-vinylsulfonyl-2-propanol, etc.), active halogen compounds (e.g., 2,4-dichloro-6-hydroxy
  • the photographic light-sensitive material according to the present invention may contain in its photographic emulsion layers or other constituent layers various surfactants for various purposes such as improvement of coating properties, antistatic properties, slipping properties, emulsion dispersibility, anti-adhesion properties, and photographic properties (for example, development acceleration, increase in contrast, sensitization, etc.).
  • various surfactants for various purposes such as improvement of coating properties, antistatic properties, slipping properties, emulsion dispersibility, anti-adhesion properties, and photographic properties (for example, development acceleration, increase in contrast, sensitization, etc.).
  • the light-sensitive material according to the present invention may contain in its photographic emulsion layers color-forming couplers, that is, compounds capable of forming color by oxidative coupling with an aromatic primary amine developing agent (for example, a phenylenediamine derivative or an aminophenol derivative) in color development processing.
  • color-forming couplers that is, compounds capable of forming color by oxidative coupling with an aromatic primary amine developing agent (for example, a phenylenediamine derivative or an aminophenol derivative) in color development processing.
  • magenta couplers include 5-pyrazolone coupler, pyrazolobenzimidazole coupler, cyanoacetylcoumarone coupler, open-chain acylacetonitrile coupler, etc.
  • yellow couplers include acylacetamide couplers (e.g., benzoylacetanilides, pivaloylacetanilides, etc.), and cyan couplers include naphthol couplers, phenol couplers, etc.
  • non-diffusible couplers having a hydrophobic group called ballast group in their molecular are desirable.
  • the couplers may be of either 4-equivalent type or 2-equivalent type to silver ion.
  • DIR couplers Colored couplers having color-correcting effect or couplers capable of releasing a development inhibitor upon development (so-called DIR couplers) may also be used.
  • non-color forming DIR coupling compounds capable of forming a colorless coupling reaction product and releasing a development inhibitor and DIR redox compounds may also be incorporated.
  • the light-sensitive material according to the present invention can contain a developing agent, including those described in Research Disclosure, Vol. 176, page 29 under the item of "Developing agents".
  • the light-sensitive material prepared according to the present invention may contain a dye in its photographic emulsion layers or other constituent layers as a filter dye or for various purposes such as prevention of irradiation.
  • a dye in its photographic emulsion layers or other constituent layers as a filter dye or for various purposes such as prevention of irradiation.
  • examples of such dyes include those described in Research Disclosure, Vol. 176, pages 25 to 27 under the item of "Absorbing and filter dyes".
  • the light-sensitive material according to the present invention can further contain antistatic agents, plasticizers, matting agents, lubricants, ultraviolet ray-absorbing agents, fluorescent brightening agents, air fog-preventing agents, etc. including those described in Research Disclosure, Vol. 176, pages 22 to 27 (1978).
  • Silver halide emulsion layers and/or other constituent layers are coated on a support by a procedure such as described in Research Disclosure, Vol. 176, pages 27 and 28, under the item of "Coating procedures".
  • the above-described development processing was initiated using 500 ml of each of the mother solutions for processing solutions having the compositions described below and subsequently carried out continuously under the replenish procedure wherein each of the replenishers for processing solutions having the compositions described below was replenished to the processing solution at the rate shown in Table 1 below per roll of the above-described color negative film of 24 exposures processed until 80 rolls of the films was processed. A number of rolls processed before the occurrence of precipitate in the bleaching solution was observed with the naked eye was determined.
  • composition of each processing solution used in the above-described processing is set forth below.
  • the use of the bleach accelerating agent together with the compound represented by the general formula (I-a) or (I-b) in the bleaching solution according to the present invention provides excellent properties in that the accelerating function for removing silver is not affected and in that the precipitate is not formed in the bleaching solution even though a large number of color light-sensitive materials are continuously processed.
  • the above-described development processing was initiated using 500 ml of each of the mother solution for processing solutions having the compositions described below and subsequently carried out continuously under the replenish procedure wherein each of the replenishers for processing solutions having the compositions described below was replenished to the processing solution at the rate shown in Table 3 below per roll of the above-described color reversal film of 36 exposures processed until 100 rolls of the films were processed. The number of rolls processed before the occurrence of a precipitate in the bleaching solution was observed with the naked eye was determined.
  • composition of each processing solution used in the above-described processing is set forth below.
  • the use of the bleach accelerating agent together with the compound represented by the general formula (I-a) or (I-b) in the bleaching solution according to the present invention provides in the reversal processing system excellent properties in that the accelerating function for removing silver is not damaged and in that the precipitate is not formed in the bleaching solution even though a large number of color light-sensitive materials are continuously processed.

Landscapes

  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)
US06/680,115 1983-12-12 1984-12-10 Method for processing color photographic light-sensitive material Expired - Lifetime US4546070A (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP58-233844 1983-12-12
JP58233844A JPS60125843A (ja) 1983-12-12 1983-12-12 カラ−写真感光材料の処理方法

Publications (1)

Publication Number Publication Date
US4546070A true US4546070A (en) 1985-10-08

Family

ID=16961449

Family Applications (1)

Application Number Title Priority Date Filing Date
US06/680,115 Expired - Lifetime US4546070A (en) 1983-12-12 1984-12-10 Method for processing color photographic light-sensitive material

Country Status (4)

Country Link
US (1) US4546070A (de)
EP (1) EP0146087B1 (de)
JP (1) JPS60125843A (de)
DE (1) DE3472311D1 (de)

Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4596764A (en) * 1984-07-03 1986-06-24 Fuji Photo Film Co., Ltd. Method of processing image-wise exposed silver halide color photographic material
DE3642244A1 (de) * 1985-12-11 1987-06-19 Fuji Photo Film Co Ltd Farbphotographisches silberhalogenidmaterial und verfahren zu dessen behandlung
US4707434A (en) * 1984-08-20 1987-11-17 Konishiroku Photo Industry Co., Ltd. Color image forming method comprising processing with a bleach-fixing solution
US4745048A (en) * 1985-06-07 1988-05-17 Fuji Photo Film Co., Ltd. Silver halide color photographic material and method of processing the same using an improved desilvering accelerator
US4780398A (en) * 1986-08-28 1988-10-25 Olin Hunt Specialty Products, Inc. Bleaching composition and process for color photographic materials
US4822725A (en) * 1984-05-21 1989-04-18 Fuji Photo Film Co., Ltd. Method for bleaching color photographic material
US4845017A (en) * 1984-07-10 1989-07-04 Fuji Photo Film Co., Ltd. Method for processing silver halide color photographic light-sensitive material
US4908300A (en) * 1985-07-18 1990-03-13 Konishiroku Photo Industry Co., Ltd. Method of processing silver halide color photographic material
US4914008A (en) * 1985-04-25 1990-04-03 Konishiroku Photo Industry Co., Ltd. Processing method of light-sensitive silver halide color photographic material
US4914009A (en) * 1986-06-30 1990-04-03 Fuji Photo Film Co., Ltd. Process for forming direct positive color image comprising the use of bleach accelerators
US5298370A (en) * 1991-05-14 1994-03-29 Fuji Photo Film Co., Ltd. Method of processing silver halide color photographic material and photographic bleach-fixing composition
WO1996007676A1 (en) * 1994-09-06 1996-03-14 Ekagen Corporation Polymeric resin for disulfide bond synthesis
US5695915A (en) * 1991-09-11 1997-12-09 Konica Corporation Processing method for silver halide color photographic light-sensitive material

Families Citing this family (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4990652A (en) * 1985-10-03 1991-02-05 Atochem North America, Inc. Intermediates for preparing multifunctional thiadiazole lubricant additives
DE223916T1 (de) * 1985-10-03 1987-10-15 Pennwalt Corp., Philadelphia, Pa. Mehrfach wirksame thiadiazol-additive fuer schmiermittel.
US5102568A (en) * 1985-10-15 1992-04-07 Atochem North America, Inc. Thiadiazole compounds and lubricant additives thereof
AU590628B2 (en) * 1985-10-15 1989-11-09 Fuji Photo Film Co., Ltd. Method of processing silver halide color photographic material
DE218816T1 (de) * 1985-10-15 1987-09-24 Pennwalt Corp., Philadelphia, Pa. Thiadiazolderivate und zusaetze fuer schmiermittel.
JPS6291952A (ja) * 1985-10-18 1987-04-27 Fuji Photo Film Co Ltd ハロゲン化銀カラ−写真材料の処理方法
JP2761884B2 (ja) * 1988-04-05 1998-06-04 コニカ株式会社 ハロゲン化銀カラー写真感光材料の処理方法
JP2799576B2 (ja) * 1988-10-14 1998-09-17 コニカ株式会社 ハロゲン化銀カラー写真感光材料の処理方法
JP2895878B2 (ja) * 1989-11-13 1999-05-24 富士通株式会社 モデム装置

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4033771A (en) * 1973-08-16 1977-07-05 Eastman Kodak Company Stabilized bleach-fixing baths
US4163669A (en) * 1977-04-27 1979-08-07 Mitsubishi Paper Mills, Ltd. Multilayer silver halide color photographic material
US4292401A (en) * 1979-04-12 1981-09-29 Fuji Photo Film Co., Ltd. Bleaching composition for photographic processing
US4458010A (en) * 1981-11-13 1984-07-03 Fuji Photo Film Co., Ltd. Process for bleaching color photographic sensitive materials

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3893858A (en) * 1973-03-26 1975-07-08 Eastman Kodak Co Photographic bleach accelerators
JPS5394927A (en) * 1977-01-28 1978-08-19 Fuji Photo Film Co Ltd Color photographic processing method
DE2938803A1 (de) * 1978-09-26 1980-04-03 Fuji Photo Film Co Ltd Umkehrentwicklungsverfahren fuer schwarzweissfotografische lichtempfindliche materialien
JPS5726848A (en) * 1980-07-24 1982-02-13 Fuji Photo Film Co Ltd Developing method for photosensitive silver halide material

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4033771A (en) * 1973-08-16 1977-07-05 Eastman Kodak Company Stabilized bleach-fixing baths
US4163669A (en) * 1977-04-27 1979-08-07 Mitsubishi Paper Mills, Ltd. Multilayer silver halide color photographic material
US4292401A (en) * 1979-04-12 1981-09-29 Fuji Photo Film Co., Ltd. Bleaching composition for photographic processing
US4458010A (en) * 1981-11-13 1984-07-03 Fuji Photo Film Co., Ltd. Process for bleaching color photographic sensitive materials

Cited By (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4822725A (en) * 1984-05-21 1989-04-18 Fuji Photo Film Co., Ltd. Method for bleaching color photographic material
US4596764A (en) * 1984-07-03 1986-06-24 Fuji Photo Film Co., Ltd. Method of processing image-wise exposed silver halide color photographic material
US4845017A (en) * 1984-07-10 1989-07-04 Fuji Photo Film Co., Ltd. Method for processing silver halide color photographic light-sensitive material
US4707434A (en) * 1984-08-20 1987-11-17 Konishiroku Photo Industry Co., Ltd. Color image forming method comprising processing with a bleach-fixing solution
US4914008A (en) * 1985-04-25 1990-04-03 Konishiroku Photo Industry Co., Ltd. Processing method of light-sensitive silver halide color photographic material
US4745048A (en) * 1985-06-07 1988-05-17 Fuji Photo Film Co., Ltd. Silver halide color photographic material and method of processing the same using an improved desilvering accelerator
US4908300A (en) * 1985-07-18 1990-03-13 Konishiroku Photo Industry Co., Ltd. Method of processing silver halide color photographic material
US4780403A (en) * 1985-12-11 1988-10-25 Fuji Photo Film Co., Ltd. Silver halide color photographic material containing disulfide type bleach accelerator
DE3642244A1 (de) * 1985-12-11 1987-06-19 Fuji Photo Film Co Ltd Farbphotographisches silberhalogenidmaterial und verfahren zu dessen behandlung
DE3642244C2 (de) * 1985-12-11 1998-07-02 Fuji Photo Film Co Ltd Farbphotographisches Silberhalogenidaufzeichnungsmaterial
US4914009A (en) * 1986-06-30 1990-04-03 Fuji Photo Film Co., Ltd. Process for forming direct positive color image comprising the use of bleach accelerators
US4780398A (en) * 1986-08-28 1988-10-25 Olin Hunt Specialty Products, Inc. Bleaching composition and process for color photographic materials
US5298370A (en) * 1991-05-14 1994-03-29 Fuji Photo Film Co., Ltd. Method of processing silver halide color photographic material and photographic bleach-fixing composition
US5695915A (en) * 1991-09-11 1997-12-09 Konica Corporation Processing method for silver halide color photographic light-sensitive material
WO1996007676A1 (en) * 1994-09-06 1996-03-14 Ekagen Corporation Polymeric resin for disulfide bond synthesis

Also Published As

Publication number Publication date
DE3472311D1 (en) 1988-07-28
EP0146087B1 (de) 1988-06-22
JPH0246933B2 (de) 1990-10-17
EP0146087A2 (de) 1985-06-26
EP0146087A3 (en) 1985-08-07
JPS60125843A (ja) 1985-07-05

Similar Documents

Publication Publication Date Title
US4546070A (en) Method for processing color photographic light-sensitive material
US4578345A (en) Method for processing color photographic light-sensitive material
US4524129A (en) Method for processing color photographic light-sensitive material
US4446225A (en) Method for processing color photographic light-sensitive material
US4621047A (en) Method for processing color photographic light-sensitive material
US4596764A (en) Method of processing image-wise exposed silver halide color photographic material
JPS60170853A (ja) ハロゲン化銀カラー反転写真感光材料の処理方法
US4804618A (en) Method of treating silver halide color photographic material with at least one ferric complex salt of an organic chelating compound
EP0176056B1 (de) Verfahren zur Behandlung farbphotographischer Elemente
JP2514807B2 (ja) ハロゲン化銀カラ−写真感光材料の処理方法
US4845017A (en) Method for processing silver halide color photographic light-sensitive material
US4554242A (en) Method for processing color photographic light-sensitive material
US4481290A (en) Color photographic silver halide light-sensitive materials
US4605611A (en) Method for processing silver halide color photographic material
JPS60172040A (ja) カラ−反転写真感光材料
US4508817A (en) Method of color photographic processing
US4675274A (en) Method for developing color reversal photographic materials
JPH0518103B2 (de)
JPS60244949A (ja) カラ−写真感光材料の処理方法
JPH0611805A (ja) 写真用処理組成物及び処理方法
JPS6175353A (ja) カラ−感光材料の処理方法
JPH0422948A (ja) 写真用処理組成物及び処理方法
JPH0544661B2 (de)
JPH03212639A (ja) 写真用ハロゲン化銀乳剤の製造方法
CA1282628C (en) Method for processing of color photographic elements

Legal Events

Date Code Title Description
AS Assignment

Owner name: FUJI PHOTO FILM CO., LTD., 210, NAKANUMA, MINAMI A

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST.;ASSIGNORS:KISHIMOTO, SHINZO;OHNO, SHIGERU;ABE, AKIRA;REEL/FRAME:004428/0343

Effective date: 19841127

STCF Information on status: patent grant

Free format text: PATENTED CASE

FEPP Fee payment procedure

Free format text: PAYOR NUMBER ASSIGNED (ORIGINAL EVENT CODE: ASPN); ENTITY STATUS OF PATENT OWNER: LARGE ENTITY

FPAY Fee payment

Year of fee payment: 4

FPAY Fee payment

Year of fee payment: 8

FEPP Fee payment procedure

Free format text: PAYER NUMBER DE-ASSIGNED (ORIGINAL EVENT CODE: RMPN); ENTITY STATUS OF PATENT OWNER: LARGE ENTITY

Free format text: PAYOR NUMBER ASSIGNED (ORIGINAL EVENT CODE: ASPN); ENTITY STATUS OF PATENT OWNER: LARGE ENTITY

FPAY Fee payment

Year of fee payment: 12